Original Publication Date
The Journal of Chemical Physics
DOI of Original Publication
Date of Submission
Photoelectron spectroscopy (PES) is combined with density functional theory (DFT) to study the monochromium carbide clusters CrC−n and CrCn (n=2–8). Well-resolved PES spectra were obtained, yielding structural, electronic, and vibrational information about both the anionic and neutral clusters. Experimental evidence was observed for the coexistence of two isomers for CrC−2, CrC−3, CrC−4, and CrC−6. Sharp and well-resolved PES spectra were observed for CrC−n (n=4,6,8), whereas broad spectra were observed for CrC−5 and CrC−7. Extensive DFT calculations using the generalized gradient approximation were carried out for the ground and low-lying excited states of all the CrC−n and CrCn species, as well as coupled-cluster calculations for CrC−2 and CrC2. Theoretical electron affinities and vertical detachment energies were calculated and compared with the experimental data to help the assignment of the ground states and obtain structural information. We found that CrC−2 and CrC−3 each possess a close-lying cyclic and linear structure, which were both populated experimentally. For the larger CrC−n clusters with n=4, 6, 8, linear structures are the overwhelming favorite, giving rise to the sharp PES spectral features. CrC−7 was found to have a cyclic structure. The broad PES spectra of CrC−5 suggested a cyclic structure, whereas the DFT results predicted a linear one.
Zhai, H. J., Wang, L. S., Jena, P., et al. Competition between linear and cyclic structures in monochromium carbide clusters CrC n − and CrC n (n=2–8): A photoelectron spectroscopy and density functional study. The Journal of Chemical Physics 120, 8996 (2004). Copyright © 2004 AIP Publishing LLC.
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VCU Physics Publications